Fiber-reactive, heavy metal-containing formazane dyestuffs

Abstract

Fiber-reactive, heavy metal-containing formazane dyestuffs are disclosed which are tricyclic and wherein the heavy metal is a metal of an atomic number ranging from 24 to 30 and is bonded via a --COO-- and --O-- substituent to different diazo components and to the terminal nitrogen atoms of the central formazane bridge portion ##STR1## wherein R represents an optionally substituted aliphatic hydrocarbon radical, a cycloaliphatic radical or a carbo- or heterocyclic-aromatic radical, one of the aforesaid diazo components or the radical R bearing the fiber-reactive substituent. These dyestuffs are useful for the dyeing and printing of textile materials, and also of synthetic materials for other then textile uses. The dyestuffs may contain or may be free from watersolubilizing groups the former being especially useful for the dyeing of leather, paper, and natural or synthetic polypeptide fiber materials, as well as for the dyeing and printing of material or regenerated cellulosic fiber materials, especially cotton. Dyestuffs in which this fiber-reactive substituent is a pyrimidyl amino radical containing at least one fluorine atom are distinguished by their high reactivity; dyeings or prints obtained therewith are very stable vis-a-vis acid or alkaline hydrolysis and exhibit very good fastness to light, milling and wet treatments.

We claim: 
     
       1. A dyestuff of the formula ##STR456## wherein Me 1  represents Cu, Ni, Co or Cr, A 1  represents a benzene nucleus or naphthalene nucleus substituted as shown above and further substituted by hydrogen, fluorine, chlorine or bromine, nitro, cyano, lower alkyl, phenoxy, lower alkylsulphonyl, phenylsulphonyl, sulphamoyl, N-mono-lower alkyl-sulphamoyl, N,N-di-lower alkyl-sulphamoyl, or lower alkanoyl,   R 1  represents a phenyl or naphthyl radical any substituent of which apart from any substituent (X 1  -O -M   + ) is selected from chlorine, bromine, lower alkyl or hydrogen,   R' represents hydrogen or lower alkyl,   X 1  represents --SO 2  -- or --CO--,   M +  represents hydrogen, sodium or potassium,   p represents 1 when Me 1  is Cr, and 2 when Me 1  is Cu, Co or Ni,   n represents a number varying from 1 to 7, and   Y 1  represents a fiber reactive grouping selected from   a. a radical of the formula ##STR457## wherein E 1  represents ##STR458## and, when E 1  is ##STR459## either i. R 3  represents chlorine, tri-lower alkyl-ammonio, a group of the formula ##STR460## R 4  represents a lower alkoxy, phenoxy, amino, mono-lower alkyl-amino, di-lower alkyl-amino, phenylamino, sulphophenylamino or di-sulpho-phenylamino; or   ii. both R 3  and R 4  represent chlorine, bromine or fluorine, and, when E 1  is ##STR461## R 2  represents hydrogen, fluorine, chlorine, bromine, lower alkyl, lower alkanoyl, cyano, nitro, phenyl, N-phenyl-carbamoyl or phenylsulphonyl, and each of R 3  and R 4  represents fluorine, chlorine or bromine;   b. a radical of one of the formulas ##STR462## wherein R 2  ' represents hydrogen or chlorine and either i. each of R 3  ' and R 4  ' represents chlorine or --SO 3   -M   + , or   ii. R 3  ' represents lower alkoxy, phenoxy, amino, mono-lower alkyl-amino, di-lower alkyl-amino, phenylamino, sulphophenylamino or disulphophenylamino, and R 4  ' represents tri-lower alkyl-ammonio, ##STR463## R 5  represents hydrogen or lower alkyl; c. 2,3-dichloro- or 2,3-dibromo-quinoxaline-6-carbonyl;   d. 2,3-dichloro- or 2,3-dibromo-quinoxaline-6-sulphonyl;   e. 1,4-dichloro- or 1,4-dibromo-phthalazine-6-carbonyl;   f. 2,4-dichloro- or 2,4-dibromo-quinazoline-6-carbonyl;   g. 2,4-dichloro- or 2,4-dibromo-quinazoline-7-carbonyl;   h. [4',5'-dichloro- or 4',5'-dibromo-6'-pyridazonyl (1')]-lower alkanoyl;   i. p-[4',5'-dichloro- or 4',5'-dibromo-6'-pyridazonyl-(1')]-benzoyl;   j. a heterocyclic radical of the formula ##STR464## wherein R 6  represents chlorine, bromine or --SO 3  M + , X 1  has the same meanings as given above; and   E 2  represents sulphur or oxygen;   k. a radical of the formula ##STR465## wherein R 7  represents nitro, lower alkylsulphonyl or sulphamoyl-phenyl, and   Hal represents fluorine or chlorine in ortho- or para-position to R 7 , and   X 1  has the same meaning as above;   l. α-chloro- or α-bromo-lower alkanoyl;   m. α ,β-dichloro- or α,β -dibromo-lower alkanoyl;   n. lower alkanoyl; or   o. chloro- or bromo-lower alkenoyl.   
     
     
       2. A dyestuff as defined in claim 1, wherein A 1  represents a benzene nucleus substituted as shown in the above first formula of claim 1 and further as follows: hydrogen, the grouping -SO 3   -M   + , lower alkylsulphonyl, phenylsulphonyl, sulphamoyl, N-mono-lower alkyl-sulphamoyl, or N,N-di-lower alkyl sulphamoyl;   Me 1  represents copper,   R 1  represents phenyl substituted by hydrogen or further by one to two groupings -SO 3   -M   + , chlorine, lower alkyl;   Y 1  represents dichloropyrimidyl-(4), trichloropyrimidyl-(4) 2,4-dichloro-pyrimidyl-5-carbonyl, 2,4-dichloro-pyrimidyl-6-carbonyl, 2,4-dichloro-s-triazinyl-(6), 2-chloro-4-amino-s-triazinyl-(6), 2-chloro-4-sulphophenylamino-s-triazinyl-(6), or 2-chloro-4-lower alkoxy-s-triazinyl-(6);   R' represents hydrogen, the number of X 1  -O -M   +  groupings ranging from 2 to 4.   
     
     
       3. A dyestuff as defined in claim 2 wherein ##STR466## represents the grouping ##STR467## wherein R 10  represents -SO 3   -M   +  or lower alkylsulphonyl. 
     
     
       4. A dyestuff a defined in claim 3, wherein the group Y 1  -nr'- is in 5-position,   Y 1  represents 2,4-dichloro-pyrimidyl-5-carbonyl,   R 10  represents -SO 3   -M   + , and   R 1  represents the group ##STR468##   
     
     
       5. A dyestuff as defined in claim 3, wherein the group Y 1  -nr'- is in 5-position,   Y 1  represents 2,4-dichloro-pyrimidyl-5-carbonyl   R 10  represents -SO 3   -M   + , and   R 2  represents the group ##STR469##   
     
     
       6. A dyestuff as defined in claim 3, wherein the group Y 1  --nr'--is in 5-position,   Y 1  represents 2,4,5-trichloropyrimidyl-(6),   R 10  represents -SO 3   -M   + , and   R 1  represents the group ##STR470##   
     
     
       7. A dyestuff as defined in claim 3, wherein the group Y 1  --nr'--is in 5-position,   Y 1  represents 2,4,5-trichloropyrimidyl-(6),   R 10  represents --SO 3   -M   + , and   R 1  represents the group ##STR471##   
     
     
       8. A dyestuff as defined in claim 3, wherein the group Y 1  --nr'-- is in 4-position,   Y 1  represents 2,4-dichloro-s-triazinyl-(6),   R 10  represents --SO 3   -M   + , and   R 1  represents the group ##STR472##   
     
     
       9. A dyestuff as defined in claim 3, wherein the group Y 1  --nr' is in 5-position,   Y 1  represents 2,4-dichloro-pyrimidyl-6-carbonyl,   R 10  represents methylsulphonyl, and   R 1  represents the group ##STR473##   
     
     
       10. A dyestuff as defined in claim 2, wherein Y 1  represents the grouping ##STR474## wherein R 1  is selected from hydrogen, fluorine, chlorine bromine, lower alkyl, lower alkyl substituted by chlorine, phenyl, carbamoyl, lower alkoxy carbonyl, cyano, sulphamoyl lower alkylsulphonyl, or nitro; R 2  is selected from hydrogen, fluorine, chlorine, or bromine, lower alkyl, lower alkyl substituted by chlorine, phenyl, carbonyl lower alkyl ester group, or cyano.   
     
     
       11. A dyestuff as claimed in claim 10, wherein Y 1  represents the grouping ##STR475## wherein R 1  represents chlorine or fluorine and R 2  represents hydrogen, chlorine, bromine, or nitro. 
     
     
       12. A dyestuff as defined in claim 10 which is of the formula ##STR476## 
     
     
       13. A dyestuff as defined in claim 10 which is of the formula ##STR477## 
     
     
       14. A dyestuff as defined in claim 10 which is of the formula ##STR478## 
     
     
       15. A fiber-reactive, heavy metal-containing formazane dye of the formula ##STR479## in which R denotes a phenyl or benzoyl radical any substituent of which apart from any substituent Z or NR'--Y' is selected from fluorine, chlorine, bromine, lower alkyl or nitro; A and B each denote a phenyl radical, which radicals contain X 1   and X respectively in the o-position to the nitrogen bond, any substituent of which apart from any substituent Z and NR'--Y' is selected from lower alkyl, chlorine, bromine, nitro and lower alkylsulphonyl,   X 1  and X 2  each denote a metal-binding substituent,   Z denotes a salt-forming, water-solubilizing group exhibiting acid dissociation in water of the formula (X 1  O -M   + ) wherein X 1  represents --SO 2  -- or --CO-- and M +  represents hydrogen, sodium or potassium,   Y' denotes a pyrimidyl group of the formula ##STR480## wherein R 1  is selected from hydrogen, fluorine, chlorine, bromine, lower alkyl, lower alkyl substituted by chlorine, phenyl, carbamoyl, lower alkoxy carbonyl, or cyano, and   R 2  is selected from hydrogen, fluorine, chlorine, bromine, lower alkyl, lower alkyl substituted by chlorine, phenyl, lower alkoxy carbonyl, carbamoyl, cyano, sulphamoyl, lower alkyl sulphonyl or nitro,   R' denotes hydrogen or a lower alkyl group,   Me denotes a heavy metal of atomic numbers 24 to 29,   m denotes a positive integer from 1 to 5,   n denotes a positive integer not exceeding 2, and   Y'--nr' must be linked to a carbon atom of: a. B when X 1  is --COO-- and X 2  is --O--;   b. A or B when both X 1  and X 2  are --O--, and   c. A, B or R when both X 1  and X 2  are --COO--.     
     
     
       16. A fiber-reactive, heavy metal-containing formazane dye as defined in claim 15 which is of the formula ##STR481## 
     
     
       17. A dyestuff as defined in claim 10 which is of the formula ##STR482## wherein ##STR483## 
     
     
       18. A dyestuff as defined in claim 15, wherein Y' represents the grouping ##STR484## wherein R 1  represents fluorine or chlorine, and R 2  represents hydrogen, chlorine, bromine, or cyano,   Me represents copper or nickel, from X 1  and X 2  one X represents --COO-- and the other X --O--,   m represents 2, 3 or 4,   n represents 1, and   R' represents hydrogen, and wherein the grouping (NR'--Y--) n  is linked to B.   
     
     
       19. A dyestuff as defined in claim 18 which is of the formula ##STR485## wherein B is selected from ##STR486## and R is selected from ##STR487##